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Chem. Rev. 1993 vol 93 p.341
G. pH Effects
A common feature of photocatalytic reactions occurring on metal oxide or metal chalcogenide semiconductor powders suspended in aqueous solution is the weak dependence of the reaction rate on solution pH.  The particle size, surface charge, and band edge positions of Ti02 are strongly influenced by pH. The isoelectric point for Ti02 in water is about pH =6 and positive surface charge is expected at lower pH and negative surface charge is predicted at higher pH values. Nonetheless, changes in rate of photocatalytic activity from one end of the pH range to the other are usually small, often less than 1 order of magnitude. Despite clear evidence for the importance of surface charge on substrate adsorptivity, evidence for higher reaction rates for various photocatalytic conversions at both low pH or at high pH can be found in the literature. With Ti02 powders (anatase and rutile) suspended in aqueous silver nitrate solution, the rate of photoproduction of 0 2 and elemental Ag was affected by the solution pH. The observed pH dependence was attributed to surface-charge  ependence of Ag+ adsorption: a decrease in pH led toprotonation of either thermal or bridging surface 0- and OH groups which inhibited Ag+ adsorption to the surface. pH effects have also been shown to be significant factors in governing photoreduction (and deposition) of metals.

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Journal of Molecular Catalysis A: Chemical 227 (2005) 241¨C246
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